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org/EF Review

Solid-State Electrolytes for Sodium Metal Batteries

Zhaopeng Li, Pei Liu, Kunjie Zhu, Zhaoyuan Zhang, Yuchang Si,* Yijing Wang, and Lifang Jiao*

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batteries have been unable to satisfy the ever-increasing demands for large-scale
energy storage system. As a low-cost alternative, solid-state sodium metal batteries
(SSMBs) have shown great competitive advantages and extensive application
prospects due to their high energy density and desirable safety. However, the solid-
state electrolytes (SSEs) often possess low ionic conductivity, and the poor
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interface compatibility and inferior stability between SSEs and electrodes can result
in the continuous deterioration of the electrochemical performance. This review
summarizes the recent progresses of sodium-based SSEs, including the sodium ion
transport mechanisms of different types of SSEs, some emerging materials in
different dimensions, and interface engineering. Furthermore, the critical challenges
and new perspectives are emphasized in detail. This review provides deeper insights
to construct more comprehensive and effective SSEs for next-generation high-
performance SSMBs.

1. INTRODUCTION high safety, solid-state sodium metal batteries (SSMBs) have

The advent of advanced energy storage systems has brought been considered as one of the most promising alternatives for
human society into a brand new energy revolution, which high-performance rechargeable batteries.21,25−27 As one of the
core components, the solid-state electrolytes (SSEs) play an
changed the conventional mode for energy storage and
extremely important role to enhance the safety and electro-
conversion, especially in the area of electrochemical energy
chemical performance of SSMBs. In addition, the state-of-the-
storage systems. As one of the most promising candidates,
art SSEs should have excellent interfacial compatibility, good
sodium ion batteries (SIBs) have attracted tremendous
mechanical strength, high chemical stability, wide electro-
attention as a result of abundant reserves (∼2.74%) and low
chemical window, high Na+ transference number, low electrical
cost (∼$150 t−1) of sodium resources.1−6 Unfortunately, SIBs
conductivity, eco-friendliness, and simple preparation (Figure
still cannot meet the ever-increasing demands of high energy
1).28−32 In recent decades, the SSEs for lithium batteries have
density and long cycle life.3,7,8 More importantly, the SIBs are
made tremendous progress, which have provided a great
always facing very serious safety issues in organic liquid
valuable reference for the process of research and development
electrolyte on account of their inevitable side reactions and
of SSMBs. However, constructing appropriate SSEs with
uncontrolled dendrite growth, which will lead to continuous
excellent interfacial compatibility and superior chemical/
deterioration of the electrochemical performance, resulting in
electrochemical stability to optimize the interfacial contact
an internal short circuit, thermal runaway, and even fire.9−15 and inhibit the dendrite growth between the electrodes and
Moreover, the organic solvent still has potential hazards of SSEs are still challenging.29,31,33−35
leakage or flammability.16−21 All of these disadvantages have In this review, we outline the development history of
been severely hampering the development of SIBs in the sodium-based SSEs and elucidate the potential transport
future. It is worth noting that, when the metallic sodium foil is mechanisms of Na+ at different types of SSEs for SMBs.
used as an anode material in liquid electrolyte system, these
above phenomena will become much worse due to the high
chemical activity of sodium metal anode.1,22−24 Received: January 30, 2021
To overcome these tricky issues, many efforts have been Revised: March 10, 2021
devoted to improve the electrochemical performance of
sodium-based batteries, including designing novel electrode
materials and developing advanced battery systems. Owning to
high energy density and excellent cycling stability, especially

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Figure 1. Corresponding requirements of SSEs for SMBs.
Meanwhile, we summarize the recent progresses from different
viewpoints, including emerging materials, interface engineer-
ing, and architectural design. Furthermore, the critical
challenges and future perspectives are emphasized in detail,
which will provide deeper insight into how to construct more
comprehensive and effective SSEs for the next-generation
advanced SSMBs.
2. CLASSIFICIATION AND ION TRANSPORT
MECHANISM OF SOLID-STATE ELECTROLYTES
At present, on the basis of the differences of the Na+ transport
mechanism and chemical composition, the sodium-based SSEs
can be divided into three major categories: solid-state polymer
electrolytes (SPEs), inorganic solid-state electrolytes (ISEs),
and composite solid-state electrolytes (CSEs). Herein, their
crystal structures, ionic transport mechanisms, existing
problems and improvement strategies will be expounded in
detail in the following sections.
2.1. Solid-State Polymer Electrolytes (SPEs). As one of
the most promising SSEs, SPEs have exhibited considerable
potential in rechargeable solid-state batteries as a result of its
unique advantages, such as easy processability, excellent film-
forming ability, low interfacial resistance, and good flexibil-
ity.31,36−38 Generally, the SPEs are prepared by dissolving the
alkali metal salt into the polymer host with high molecular
weight.38 Thus, the polar functional groups are extremely
important for the dissolution of metal salts and transportation
of alkali metal ions. At present, it is widely accepted that the
alkali metal ion transport in SPEs mainly occurs in the
amorphous region of the polymer matrix, in which the motion
of long-chain segments are easier than in the crystallization
Figure 2. Na+ transport mechanism in the PEO polymer.
pubs.acs.org/EF Review
region.29,39 For example, as shown in Figure 2, Na+ can
coordinate with the polar groups of poly(ethylene oxide)
(PEO), under the action of an electric field, the motion of
long-chain segments induces sufficient free volume for Na+
migration.29,40,41 Thus, Na+ can hop from one coordination
site to the adjacent site along the polymer chains to realize the
Na+ transport.29,42
Figure 3a shows several common polymers, including PEO,
poly(acrylonitrile) (PAN), poly(vinylidene fluoride) (PVDF),
and poly(vinylidene fluoride−hexafluoropropylene) (PVDF−
HFP).43,44 Among these polymer hosts, PEO is the most
widely used polymer due to its low cost, easy accessibility, and
superior film-forming ability.21,43,45−47 However, most polymer
hosts are crystalline at ambient temperature, thus the motion
of chain segments is severely limited, resulting in poor ionic
conductivity.48−51 According to the above transport mecha-
nism, increasing the area of the amorphous region is an
effective strategy to elevate the ionic conductivity.51 Therefore,
many efforts have been made to improve it, including
copolymerization, blending, cross-linking, and doping of
additives, such as ionic liquids, plasticizers, liquid electrolyte
and inactive inorganic fillers.27,38,42,44,52−56 For example,
Panero and co-workers reported a new PEOn:sodium bis-
(trisfluoromethanesulfonyl)imide (NaTFSI) SPE with differ-
ent molar ratios.45 The results demonstrated that all SPE
membranes display high ionic conductivities in the range of
10−3 S cm−1 above 70 °C. After adding nanometric SiO2, the
mechanical properties of PEO:NaTFSI + x wt % SiO2
composite SPE were further improved. In addition, nuclear
magnetic resonance spectroscopy suggested that the SiO2 filler
may be good for the cation transference number, which was
consistent with the result of Na+ transference number
measurement. Hwang and co-workers developed a free-
standing PEO-based transparent film by adding NaClO4 and
TiO2 nanoparticles via a solution casting technique.57 The X-
ray diffraction (XRD) and Fourier transform infrared (FT-IR)
spectra results demonstrated that the crystallinity of the SPE
was gradually reduced and more PEO−Na+ complex was
generated with the increase of the NaClO4 salt. After added
nanosized TiO2 into this SPE, the amorphous region of the
SPE and the formation of the PEO−Na+ complex were further
increased (Figure 3b). When the nano-TiO2 content was 5 wt
%, the SPE with the ratio of EO/Na = 20:1 showed a
maximum ionic conductivity of 2.62 × 10−4 S cm−1 at 60 °C
(Figure 3c). In addition, a free-standing SPE film based on
PEO/PAN + NaPF6 with different dosages of nano-TiO2 was
fabricated by Sharma’s group.58 The results indicated that the
as-prepared (PEO/PAN) 20 + NaPF6 + 15 wt % TiO2
composite film exhibited optimized ionic conductivity of 1.8
× 10−4 S cm−1.
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Figure 3. (a) Structural formulas of common polymer-based electrolytes. (b) Schematic of Na+ conduction and (c) ionic conductivity plots of pure
PEO, PEO−NaClO4, and 5% TiO2-blended nCPE.57 This figure was reproduced with permission from ref 57. Copyright 2014 Elsevier. (d)
Chemical compositions of a novel CPE: cross-linker, PEG, and the sodium salt.27 This figure was reproduced with permission from ref 27.
Copyright 2018 Wiley-VCH. (e) Temperature-dependent comparison of ionic conductivity of B-CPE, C-CPE, and PEO-SPE. (f) Schematic of the
c-NFM/B-CPE/Na solid-state battery assembled by the one-step in situ solidification method.59 This figure was reproduced with permission from
ref 59. Copyright 2020 Elsevier.

In comparison to the SPEs, the composite polymer
electrolytes (CPEs) exhibited more excellent performances.
For instance, Li and co-workers reported a network-based CPE
by polymerizing amine-terminated polyethylene glycol (PEG)
and octakis(3-glycidyloxypropyldimethylsiloxy)-
octasilsesquioxane (octa-POSS) in existence with NaClO4
(Figure 3d).27 The differential scanning calorimetry results
showed that the glass transition temperature (Tg) of the CPE
gradually increased with the increase of the NaClO 4
concentration, which can be ascribed to the coordination
interaction between Na+ and PEO chains, leading to
suppressed segmental motion of the polymer matrix. Electro-
chemical impedance spectroscopy (EIS) analysis was con-
ducted to investigate the ionic conductivity of the CPE, which
indicated that POSS−4PEG2K(NaE16) with a molar ratio of
EO/Na = 16:1 displayed the highest ionic conductivity of 2.56
× 10−4 S cm−1 at 80 °C. Furthermore, to further improve the
ionic conductivity and enhance the interfacial compatibility of
CPE, Ma’s group prepared a novel three-dimensional (3D)
CPE containing anion-trapping boron (B-CPE) by in situ
polymerizing the oligo(ethylene glycol) methyl ether meth-
acrylate (PEGMA) monomer and boron-containing 2-hydrox-
yethylmethacrylate (B-HEMA) cross-linker inside a supporting
matrix.59 Benefiting from the low Tg of PEGMA and the Lewis
acid effect of the boron atom, the B-CPE displayed a superior
ionic conductivity of 0.26 S cm−1 at 40 °C (Figure 3e), wide
voltage window of 5.1 V, and high Na+ transference number of
0.66 compared to PEO-based SPE and C-CPE (without
boron). As shown in Figure 3f, to decrease the interface
resistance and promote the transport efficiency of Na+ at the
electrode/electrolyte interface, a novel composite Na-
Ni1/3Fe1/3Mn1/3O2 (C-NFM) cathode was fabricated by in
situ solidification of B-CPE inside the NFM cathode via heat-
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induced polymerization. The SSMBs with configurations of c-
NFM/B-CPE/Na exhibited excellent cycling stability and good
rate capability.
Until now, SPEs still suffer from insufficient room-
temperature ionic conductivity, low mechanical strength, and
inferior electrochemical stability, which greatly restrict their
practical application. Therefore, it is not enough to improve
the comprehensive performance of the SPEs by facile co-
blending, copolymerization, or cross-linking. The Na+ trans-
port mechanism of SPEs should be further explored and
studied to elucidate the intrinsic connection between the Na+
and the polymer host. At the same time, the prescription
composition and manufacturing process should be further
optimized toward high-performance polymer-based SSMBs.
2.2. Inorganic Solid-State Electrolytes (ISEs). In
comparison to the SPEs, ISEs usually possess high ionic
conductivity at room temperature (≥10−4 S cm−1), high Na+
transference number (close to 1), wide electrochemical
window (≥4.5 V) and high shear modulus.42 In addition, the
ISEs exhibit high mechanical strength, which can effectively
inhibit the growth of sodium dendrites. However, the poor
interfacial compatibility/stability between electrodes and rigid
ISEs greatly restricts the interfacial Na+ transport and induced
the inevitable side reactions, leading to a large interfacial
resistance.60−63 At present, the crucial factor of ISEs is not the
ionic conductivity but the interface compatibility and stability
between electrode and electrolyte, which have become the
bottleneck for further development of SSMBs.31 In general, the
Na+ vacancies or interstitials are considered as the effective
charge carriers for Na+ diffusion in ISEs. The principal
migration mechanism of Na+ in the crystalline ISEs mainly has
three types: (1) Vacancy diffusion mechanism: the mobile
charged species need to migrate or hop from one vacant site to
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Figure 4. Crystal structures of Na−β/β″-Al2O3.31 This figure was reproduced with permission from ref 31. Copyright 2018 Elsevier.
the adjacent vacant site. (2) Direct interstitial mechanism: the
mobile species with a small size can hop from one interstitial
site to the unoccupied neighboring interstitial site. (3)
Correlated interstitialcy mechanism: migration interstitial
Na+ can enter into the adjacent site by substituting the
adjacent lattice ion.60 Therefore, the charge carrier concen-
tration, diffusion type, defect concentration, and migration
path greatly influence the thermodynamics and kinetics of Na+
conduction in the crystal structures of the ISEs. In recent
decades, the widely studied ISEs for sodium-based batteries are
mainly focused on the oxide-based SSEs (Na−β-alumina
electrolyte and sodium superionic conductor electrolyte) and
sulfide-based SSEs.
2.2.1. β-Alumina Electrolyte. Owing to high ionic
conductivity and superior thermal properties, β-alumina was
first applied in high-temperature Na−S batteries and achieved
favorable results in the 1960s,31,64 and then it was used as an
electrolyte in large-scale energy storage systems. According to
the difference of chemical composition and O2− stacking
sequence, β-alumina can be divided into two different crystal
structures: β-Al2O3 (hexagonal; P63/mmc; a = b = 5.58 Å; and
c = 22.45 Å) and β″-Al2O3 (rhombohedral; R3̅m; a = b = 5.61
Å; and c = 33.85 Å).31,64−67 Both of them are made up of the
Na+ conduction plane and Al−O spinel block by alternating
arrangement (Figure 4). The chemical formula of β-Al2O3 is
Na2O·xAl2O3 (x = 8−11), which is composed of two spinel
blocks and one Na + conduction plane, and each Na +
conduction plane just has one Na+, while β″-Al2O3 with a
general formula of Na2O·xAl2O3 (x = 5−7) contains three
spinel blocks and two Na+ conduction planes, and each
conduction plane has two Na+, illustrating that the lattice
volume and Na+ content of β″-Al2O3 are bigger than those of
Na−β-Al2O3; this is the reason why the ionic conductivity of
β″-Al2O3 is higher than that of β-Al2O3.31,68
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However, β″-Al2O3 is a metastable phase in thermody-
namics, which will induce irreversible crystal transformation
and precipitate the impurities (for example, β-Al2O3 and
NaAlO2) in a high temperature, leading to the decreased ionic
conductivity and increased grain-boundary resistance dramat-
ically.31,69,70 Therefore, many efforts have been made based on
the chemical doping by introducing new component into the
β″-Al2O3 structure to stabilize the crystal structure and
promote the densification. For example, Chen and co-workers
synthesized a high-performance β″-Al2O3 electrolyte by doping
MgO via a solid-state reaction.67 The results showed that the
MgO dopant can significantly improve the densification of β″-
Al2O3 ceramics by decreasing the sintering temperature. At the
same time, they found that 1550−1580 °C was the optimum
sintering temperature range for optimizing the microstructure
and eliminating the abnormal grain growth. According to the
results of XRD, scanning electron microscopy (SEM), and EIS,
the increased ionic conductivity of β″-Al2O3 electrolytes with
increasing MgO doping content is mainly ascribed to the grain
growth of the β″ phase and the increased Na+ concentration.
As a result, when the doping content of MgO was 0.4 wt % and
the sintering temperature was 1550 °C, the as-prepared β″-
Al2O3 electrolyte exhibited the optimal bending strength and
relatively low activation energy. In addition, there are many
other stabilizers that have been added to the reaction system to
promote the ionic conductivity of β″-Al2O3 electrolytes, such
as TiO2, Nb2O5, NiO, MnO2, Y2O3, etc.29,71−74
More importantly, even if the high-purity β″-Al2O3 phase
displays excellent ionic conductivity, the mechanical property
and moisture sensitivity make it become an inferior
candidate.66,75,76 Therefore, it is still challenging for the β″-
Al2O3 electrolyte to find the optimal trade-off between high
ionic conductivity and excellent mechanical strength.
2.2.2. Sodium Superionic Conductor (NASICON) Electro-
lyte. The NASICON electrolyte has been extensively studied
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Figure 5. Crystal structures of NASICON with (a) rhombohedral phase and (b) monoclinic phase.31 This figure was reproduced with permission
from ref 31. Copyright 2018 Elsevier. (c) Four different Na+ ion transport pathways in the monoclinic NASICON structure.88 This figure was
reproduced with permission from ref 88. Copyright 2016 American Chemical Society. (d) BEVL maps of the NZSP systems. (e) Local enlarged
drawing of bottlenecks C, D, E, and F in the Na1−Na3−Na1 channel. (f) Comparison charts of size of different bottlenecks in the Na1−Na3−Na1
channel for NZP and Zn0.1 system.35 This figure was reproduced with permission from ref 35. Copyright 2020 American Chemical Society. (g)
Low-resolution image of La distribution and (h) high-resolution elemental distribution images of La, P, Zr, and Si based on the synchrotron X-ray
nanoprobe analysis. (i) Total conductivity versus relative density of Na3+xLaxZr2−xSi2PO12 with different x values. (j) Arrhenius plots of
Na3+xLaxZr2−xSi2PO12 (x = 0, 0.10, 0.20, 0.30, and 0.40).89 This figure was reproduced with permission from ref 89. Copyright 2016 Wiley-VCH.

over the past few decades as a result of its relatively high room-
temperature ionic conductivity, superior thermal stability, and
wide electrochemical window.28,77−81 This is principally
because the NASICON electrolyte possesses a unique 3D
open framework with continuous diffusion paths, which can
significantly accelerate the Na+ transport. The general formula
of NASICON-type electrolyte is Na1+xZr2SixP3−xO12 (0 ≤ x ≤
3), which was first proposed by Hong and Goodenough in
1976 and demonstrated its skeleton structure for fast Na+
transport.82−84 Among Na1+xZr2SixP3−xO12 (0 ≤ x ≤ 3)
electrolytes, Na3Zr2Si2PO12 (x = 2) shows the highest ionic
conductivity in order of ∼10−4 S cm−1 at room temperature
and ∼10−1 S cm−1 at 300 °C.80,85−87 Figure 5 exhibits two
different crystal structures of Na3Zr2 Si2 PO 12 (NZSP),
rhombohedral and monoclinic phases, in which ZrO 6
octahedra and SiO4/PO4 tetrahedra are interconnected by
corner-sharing.31 In the rhombohedral phase, two distinct Na
sites (Na1 and Na2) construct an open 3D framework (Figure
5a), while a slight lattice distortion changes its crystal phase to
a monoclinic phase and splits the Na2 site into two sites (Na2
and Na3) (Figure 5b).31 As shown in Figure 5c, there are four
different migration channels for the diffusion of Na+ in the
monoclinic NASICON structure, including two Na1−Na2 and
two Na1−Na3 channels.88 Na+ must transfer through the
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triangular bottleneck region, which means that the size of the
bottleneck directly influences the diffusion of Na+ in it.35
Therefore, many efforts have been devoted to enlarge the
size of the bottleneck region. For example, numerous voids or
excess Na+ were introduced to increase the concentration of
charge carriers, and elemental doping/substitution was
conducted using multivalent cations (for example, Zn2+, La3+,
Ca2+, Sc3+, and Mg5+) to reduce the diffusion barrier of Na+ by
enlarging the size of the bottleneck of Na+ migration
channels.35,85,89−91 For instance, Yao and co-workers reported
a dense NASICON-type Na3.4Zr1.9Zn0.1Si2.2P0.8O12 electrolyte
by simultaneous substitution of the P5+ and Zr4+ sites with Si4+
and Zn2+, respectively.35 According to the geometric analysis of
the neutron powder diffraction date, the Zr4+ site substitution
by Zn2+ can modify the bottleneck size in the Na1−Na3−Na1
channel and increase the Na+ content in the NASICON
structure (panels d−f of Figure 5). Thus, the
Na3.4Zr1.9Zn0.1Si2.2P0.8O12 electrolyte showed a record high
ionic conductivity of 5.27 × 10−3 S cm−1 at room temperature.
Hu’s group developed a new NASICON-type electrolyte by
doping La3+ in the NASICON structure.89 As shown in panels
g and h of Figure 5, the synchrotron X-ray nanoprobe analysis
results confirmed that self-formed several new phases of
Na3La(PO4)2, La2O3, and LaPO4 accumulated at the grain
boundary, which can manipulate the Na+ concentration of the
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Figure 6. Crystal structures of Na3PS4 with (a) cubic phase and (b) tetragonal phase.31 This figure was reproduced with permission from ref 31.
Copyright 2018 Elsevier. Na3PS4 structure of (c) cubic and (d) tetragonal phases in the (010) plane.100 This figure was reproduced with permission
from ref 100. Copyright 2018 American Chemical Society. (e) Unit cell structure and (f) 3D bond valence map isosurfaces of the Na3SbS4
structure.101 This figure was reproduced with permission from ref 101. Copyright 2016 Wiley-VCH. (g) Crystal structure of Na3SbS4 viewed along
the c axis and (h) coordination environments of Na1 and Na2 atoms.97 This figure was reproduced with permission from ref 97. Copyright 2016
Wiley-VCH. (i) Crystal structure of Na3PSe4 and the sodium ion diffusion channels formed by PSe4 tetrahedra. (j) Fourier map of the difference
pattern at the xy plane.94 This figure was reproduced with permission from ref 94. Copyright 2015 Wiley-VCH. (k) Illustration of Na···Na
interatomic correlations in the crystal structure of Na11Sn2PS12. Large green spheres represent unoccupied vacancies formed by Na+.102 This figure
was reproduced with permission from ref 102. Copyright 2018 Wiley-VCH.

NASICON phase, regulate the chemical composition of the
grain boundary, and elevate the relative density of the ceramic
slices. When the value of x reaches up to 0.3, the NASICON-
type composite electrolyte of Na3.3Zr1.7La0.3Si2PO12 exhibited
an ultrahigh ionic conductivity of 3.4 × 10−3 S cm−1 at room
temperature (panels i and j of Figure 5), which was about 5
times to that of NZSP (6.7 × 10−4 S cm−1). Ruan et al. also
confirmed that the ionic conductivity of the NZSP electrolyte
can be greatly affected by the aliovalent substitution of Zr4+
sites in ZrO6 octahedra with rare earth metal, such as La3+,
Nd3+, and Y3+.92 The charge imbalance can accelerate the
mobility of Na+ in the NZSP lattice, leading to a higher ionic
conductivity compared to the pure NZSP electrolyte.
Similar to Na-β/β″-Al2O3 electrolytes, the NASICON-type
electrolytes still have the same bottleneck problem, which is
the poor interfacial compatibility between electrode and
electrolyte. The rigid interfacial contact severely limits the
interfacial stability, leading to pulverization of the electrode
material and rapid degradation of the electrochemical perform-
ance. Furthermore, the insufficient ionic conductivity at
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ambient temperature of oxide-based SSEs and the large
interfacial resistance between cathode and electrolyte have
not been fundamentally solved. Therefore, constructing a
stable and flexible interface between the oxide-based electro-
lyte and the electrode is an extremely important solution to
improve the harsh interfacial contact and accommodate
dramatic volume change of electrode material during repeated
cycles.
2.2.3. Sulfide-Based Solid-state Electrolytes. As a result of
the large ionic radius and high polarizability of the S atom, the
electrostatic interaction between Na+ and the skeleton can be
weakened greatly. Thus, the sulfide-based SSEs exhibit higher
ionic conductivity at ambient temperature compared to the
analogous oxide-based SSEs.29,93 As one of the most promising
candidates, the sulfide electrolytes have attracted great
attention because of its many advantages besides high ionic
conductivity, such as moderate synthetic conditions, lower
grain-boundary resistance, etc.94−98 Among various types of
sulfide-based electrolytes, the Na3PS4 electrolyte is one of the
most widely studied sulfide electrolytes by now. As shown in
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panels a and b of Figure 6, the Na3PS4 electrolyte has two
different structural polymorphs: cubic phase (I4̅3m; a = b = c =
7.0699 Å) and tetragonal phase (P4̅21c; a = b = 6.9520 Å; and
c = 7.0757 Å).31,99 The existing form of the Na3PS4 electrolyte
is the tetragonal phase, which can be transformed into the
cubic phase at high temperature.29
As shown in panels c and d of Figure 6, Zeier’s group
fabricated the Na3PS4 electrolyte with cubic and tetragonal
phases by ball-milling and high-temperature routes, respec-
tively.100 Rietveld refinements and synchrotron pair distribu-
tion function (PDF) analyses were applied to verify their
average and local structures. Even though Rietveld analysis
confirmed the difference in the average structure of the cubic
phase and tetragonal phase, the PDF results showed that both
Na3PS4 polymorphs have the same tetragonal structural motif
on the local scale. This work revealed that the difference in
ionic conductivity of the Na3PS4 electrolyte was not derived
from the crystal structures but related to the defect
concentration. Thus, in order to promote the ionic
conductivity of sulfide electrolytes, more defects need to be
created by aliovalent doping/substitution in S2− sites or P5+
sites to introduce more Na+ vacancies or interstitials.
Moreover, the appropriate channel size is another crucial
factor for fast Na+ diffusion; a too large or too small channel
size will restrict the diffusion process of Na+. Jung and co-
workers reported a new type tetragonal Na3SbS4 superionic
conductor with 3D Na+ diffusion channels via a scalable
solution process.101 Figure 6e shows the crystal structure of the
Na3SbS4 electrolyte with a unit cell, which is composed of a
body-centered tetragonal structure of SbS43− tetrahedra, and
these SbS43− tetrahedra are interconnected with neighboring
tetrahedra by Na+. Meanwhile, all of the Na+ diffusion channels
are aligned perpendicular to the [010] plane. The bond valence
sum mapping (BVSM) was applied to further understand the
3D Na+ diffusion channels of the Na3SbS4 electrolyte (Figure
6f), which confirmed the 3D network through-hole structure
for Na+ conduction. EIS results illustrated that the Na3SbS4
electrolyte displayed a high conductivity of 1.1 × 10−3 S cm−1
at 25 °C, a low activation energy of 0.20 eV, and excellent
structural stability in dry air. Zhang’s group also synthesized
sodium superionic conductor Na3SbS4 with a tetragonal
structure.97 Figure 6g shows the crystal structure of tetragonal
Na3SbS4 in terms of the Rietveld refinement of the powder
XRD results. The unit cell consists of two SbS4 tetrahedral
structures, in which the Sb atoms and S atoms are located at
the 2b and 8e sites, respectively. Figure 6h exhibits the
coordination environments of Na1 and Na2 sites. The
refinement results demonstrated that the unit cell of the
Na3SbS4 electrolyte have been expanded as a result of the
distortion of sulfur sublattices and the existence of Na
vacancies (2.5 mol %). Profiting from the improved structural
features, the Na3SbS4 electrolyte achieved a record high ionic
conductivity of 3.0 × 10−3 S cm−1 at room temperature.
Furthermore, Zhang and co-workers reported a novel Na3PSe4
electrolyte by replacing sulfur with selenium (Se) and
investigated its crystal structure and performance parameters.94
As shown in Figure 6i, the crystal structure of Na3PSe4 was
detected as a cubic phase. The Na3PSe4 unit cell was revised by
Rietveld refinement with a lattice parameter of a = 7.309 Å,
which was much larger than that of cubic Na3PS4. The 3D
framework demonstrated that the fast diffusion of Na+ could
happen in the interstitial space of PSe4 tetrahedron by Na+
hopping across the conduction pathways. The Fourier map
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(Figure 6j) of the difference pattern in the xy plane (z = 0)
illustrated that the largest residual density was located at the
site of 12d, in which some Na+ occupied this site and
constructed continuous 3D Na+ diffusion pathways. Owing to
the large ionic radius and high polarizability of the Se ion, the
electrostatic attractive force between Na+ and PSe4 tetrahedron
was weakened apparently and more interstitial Na+ were
created, resulting in a high ionic conductivity of 1.16 × 10−3 S
cm−1 at room temperature. Roling and co-workers presented a
novel superionic conductor Na11Sn2PS12 electrolyte by
annealing Na3PS4 and Na4SnS4 pure phases at high temper-
ature. 102 As shown in Figure 6k, the high-speed Na +
conduction in the Na11Sn2PS12 electrolyte was mainly derived
from the existence of Na+ vacancies, which can interconnect
these ion diffusion paths into a continuous 3D Na+ migration
channel, endowing the Na11Sn2PS12 electrolyte with a high
ionic conductivity of 3.7 ± 0.3 mS cm−1 at room temperature.
Even though the sulfide-based SSEs possess high ionic
conductivity and adequate deformability, the poor ambient
stability always restricts their further development and large-
scale application. Most of the sulfide electrolytes are sensitive
to atmospheric moisture and oxygen as a result of the relatively
weak P−S bonds.29,94,103,104 When exposed to a humid
environment, the sulfide-based SSEs can decompose and
release toxic H2S gas rapidly, resulting in a dramatic decrease
of ionic conductivity.94,105 Therefore, to promote the ambient
stability of the sulfide electrolytes, the weak P−S bonds must
be replaced by aliovalent ion substitution to strengthen the
bonding interactions between S atom and doping element. For
example, Shang et al. reported a new sulfide-based superionic
conductor Na3P1−xAsxS4 electrolyte by partial substitution of P
sites with alloying element arsenic (As).106 The fundamental
reason for excellent phase and moisture stability was
investigated by integrating the first principles with experiments,
which elucidated that the enhanced moisture stability of the
Na3P1−xAsxS4 electrolyte mainly originated from the weaker
As−S affinity compared to that of P−O, resulting in a shifting
of the reaction products from easy-forming oxysulfides to
difficult-forming hydrates.
In addition, the sulfide electrolytes also present poor
interface compatibility and limited electrochemical stability,
which triggers a series of interfacial side reactions on the
electrode/electrolyte interface and induces the notorious
dendrite growth.61 Thus, it is necessary to boost the
electrochemical stability by designing new types of sulfide-
based SSEs.
2.3. Composite Solid-State Electrolytes (CSEs). To
overcome the interfacial compatibility between ISEs and
electrodes, the best compromise solution has been suggested
to address these challenging problems, that is, integrating the
high ionic conductivity of ISEs with the flexibility of SPEs into
a composite material system.33,48,84,107 Many researchers have
revealed that the CSE system is a very promising solution for
developing high-performance SSEs as a result of the synergistic
effect between the ceramic electrolyte and the polymer matrix.
Chen and co-workers developed a solvent-free ceramic/
polymer CSE with good flexibility and high ionic conductivity
for SMBs.107 When the content of the ceramic filler (NZSP)
reached up to 40 wt %, a high ionic conductivity of 2.4 mS
cm−2 can be obtained at 80 °C. Furthermore, this CSE showed
superior thermal stability (20−150 °C) and good electro-
chemical performance. Dalvi’s group reported a NZSP-based
CSE by mechanical mixing the NZSP nanoparticles with a
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Energy & Fuels pubs.acs.org/EF Review

Figure 7. Na+ transport model schematic in the (a) PEO-based CSE and (b) NZSP-based CSE.26 This figure was reproduced with permission from
ref 26. Copyright 2019 Elsevier. Schematic of (c) randomly dispersed ceramic particles and (d) vertically aligned and connected ceramic channels
in the polymer matrix.109 This figure was reproduced with permission from ref 109. Copyright 2017 American Chemical Society. The preparation
process of the SiO2-aerogel-reinforced CPE: (e) 3D SiO2 aerogel framework and (f) SiO2 aerogel−PEO CSE.110 This figure was reproduced with
permission from ref 110. Copyright 2018 Wiley-VCH. Schematic of the ionic conduction mechanism in CSE: (g) conventional discontinuous
ceramic filler and (h) 3D interconnected ceramic filler.111 This figure was reproduced with permission from ref 111. Copyright 2018 Elsevier. The
possible conduction mechanism in CSE with (i) agglomerated ceramic nanoparticles and (j) 3D continuous ceramic framework.112 This figure was
reproduced with permission from ref 112. Copyright 2018 Wiley-VCH. (k) Structure and Na ion transportation channels of ANs−GPE.113 This
figure was reproduced with permission from ref 113. Copyright 2019 Springer Nature.

PEO-based polymer electrolyte.108 The Na+ transport
mechanism was investigated by combining EIS analysis and
X-ray absorption near edge structure spectroscopy, which
illustrated the decoupling effect of Na+ from the PEO matrix
and decisive role of NZSP for Na+ conduction. The CSE
displayed a low interface resistance, relative high ionic
conductivity (10−4 S cm−1), and wide electrochemical window
(4.64 V versus Na+/Na). In addition, Fan’s group also
fabricated two different types of PEO/NZSP flexible CSE
membranes (PEO- and NZSP-based composite electrolytes)
by the solution-casting method and proposed a new Na+
transport model (panels a and b of Figure 7),26 which
illustrated that there are three pathways for Na+ diffusion in
CSE based on the difference of the ceramic filler content: (1)
PEO ion conductor, (2) polymer/ceramic interface, and (3)
ion hopping among the ceramic particles. The optimal PEO/
NZSP CSE presented a high ionic conductivity of 1.5 × 10−4 S
cm−1 at 55 °C and excellent electrochemical stability (4.8 V
versus Na+/Na). For this kind of CSE fabricated by facile
physical mixing, Goodenough and co-workers proposed a new
thinking to demonstrate the transfer process of CSE.36 That is,
the transfer process of CSE is constantly changed from
“ceramic-in-polymer”, “intermediate”, to “polymer-in-ceramic”
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with the increase of the ceramic content in the polymer matrix.
In this type of CSE, the active ceramic fillers play a vital role in
facilitating ion tranport and promoting ionic conductivity,
which is because the ceramic particles possess high Na+
conduction ability and increase the motion ability of polymer
chains by forming more amorphous regions in the polymer
host. As a result, the CSE exhibited enhanced interface stability
and excellent electrochemical performance. In terms of the
practical application, the “ceramic-in-polymer” CSEs are more
adaptive to the small-scale flexible devices as a result of the low
cost and good flexibility, while the “polymer-in-ceramic” CSEs
are more suitable for large-scale energy storage systems.36
However, most of the CSEs are based on facile mechanical
mixing without architecture design, which will cause two
critical problems: (1) agglomerated ceramic fillers, which
cannot form a 3D network with continuous diffusion paths for
Na+ migration, leading to a constrained ionic conductivity at
ambient temperature; (2) Insufficient interfacial contact
between ceramic fillers and polymer matrixes, which will
block the diffusion of Na+ from the ceramic to polymer phase,
leading to an increased interfacial resistance for CSE bulks. To
solve these problems, some novel CSEs with continuous ion
conduction pathways have been successfully designed and
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Energy & Fuels pubs.acs.org/EF Review

Figure 8. Schematic of the composite cathode with (a) incomplete ionic contacts and (b) favorable ionic contacts.89 This figure was reproduced
with permission from ref 89. Copyright 2016 Wiley-VCH. (c) Illustration of the reactive Na anode/sulfide-based SSE interface and stable Na
anode@alucone/sulfide-based SSE interface. (d) 3D rendering models of the Na@mld150C anode based on the depth scan by ToF-SIMS. (e)
ToF-SIMS depth profiles of the cycled Na@mld150C electrode. (f) Na platting/stripping behavior of Na@mld150C and bare Na symmetric cells
at 0.1 mA cm−2 with a capacity of 0.1 mAh cm−2.93 This figure was reproduced with permission from ref 93. Copyright 2020 Wiley-VCH. (g)
Contact model between the ceramic pellet electrolyte and sodium metal anode. (h) Good wetting ability after introducing the artificial interlayer
during the plating of sodium.127 This figure was reproduced with permission from ref 127. Copyright 2017 American Chemical Society. (i)
Schematic of the sodium plating behavior on the G−NASICON interface. (j) TEM image of G−NASICON. (k) Na plating/stripping cycling
stability of symmetric cells with bare NASICON and G−NASICON electrolyte.126 This figure was reproduced with permission from ref 126.
Copyright 2019 American Chemical Society.

achieved significant improvement in enhancing interfacial
contact and promoting ion diffusion. Yang and co-workers
developed a flexible CSE with a vertically aligned and
interconnected ceramic network via an ice-templating proc-
ess.109 In comparison to the random dispersed ceramic
particles in the PEO matrix (Figure 7c), the new type CSE
with a vertically aligned and connected ceramic network
displayed a higher ionic conductivity (Figure 7d). Cui and co-
workers reported an ultrastrong reinforced CSE by introducing
an interconnected SiO2 aerogel backbone to the PEO matrix
(panels e and f of Figure 7).110 Benefiting from the unique
structure, the CSE exhibited high modulus and ionic
conductivity. Yu’s group reported a high-performance CSE
with a 3D nanostructured ceramic framework,111 which not
only endowed the high weight ratio of the ceramic filler (62 wt
%) in CSE but also provided a long-range and continuous
conduction pathway for alkali metal ions. As shown in panels g
and h of Figure 7, the internal structure of the ceramic filler has
changed from a conventional discontinuous particle filler to a
3D interconnected filler. After the voids of the 3D framework
were fully filled by polymer slurry, the novel CSE with
continuous 3D diffusion framework displayed high flexibility,
improved thermal and electrochemical stability, and excellent
interfacial compatibility. In addition, Yu and co-workers also
constructed a high-performance CSE with a 3D nanostructured
I https://doi.org/10.1021/acs.energyfuels.1c00347
hydrogel-derived inorganic ceramic framework.112 As shown in
Figure 7i, the discontinuous transfer paths were generated in
CSE due to the agglomerated ceramic particles, which lead to a
limited ionic conductivity. When the ceramic fillers were
designed as a 3D interconnected framework (Figure 7j), the
continuous interphase can significantly improve the ionic
conductivity (∼10−4 S cm−1). All of these above-described
strategies have been successfully verified in solid-state batteries
and have achieved remarkable effects in ameliorating the
interfacial compatibility, elevating the room-temperature ionic
conductivity, and optimizing the electrochemical stability.
Therefore, it is essential to construct a novel 3D
interconnected ceramic framework with continuous and fast
Na+ migration paths in the polymer matrix. Meanwhile, the
micro/nanostructures of the 3D framework can be effectively
tailored by adjusting the preparing parameters toward more
comprehensive performance. In recent years, the 3D
constructing strategy has been gradually applied in SSMBs.
For example, Kang and co-workers developed a novel CSE by
combining an inorganic ionic conductor with a gel polymer
electrolyte, in which the cross-linked β/β″-Al2O3 nanowire
membrane was tightly coated by PVDF−HFP-based gel
electrolyte (Figure 7k).113 Owning to the dense, homoge-
neous, and continuous Na+ transportation channels along the
β/β″-Al2O3 nanowires, the CSE displayed superior electro-
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Energy & Fuels
chemical stability. These unique structural designs provide new
concepts for the development of advanced SSMBs and
highlight the importance of CSE by integrating an excellent
inorganic ionic conductor with a suitable polymer into a
composite system.
By far, various SSEs have been designed and synthesized,
and their ionic conductivities have been greatly improved.
Nevertheless, the interfacial stability between ISE and the rigid
cathode still has not been fundamentally resolved, and the
growth of sodium dendrites has not been completely
restrained. More importantly, the potential transport mecha-
nisms and dynamic diffusion process of Na+ in SSEs still need
to be explored more deeply. At present, the single SSE system
has been unable to meet the ever-increasing demands for
practical application. Thus, developing new types of composite
electrolytes with comprehensive properties are the key and
premise to achieve the ultimate goal of commercialization for
SSMBs. Meanwhile, by combination of the computing
simulation and chemical engineering, we can make a more
reasonable prediction regarding the theoretic structure of our
target materials and regulate the optimal composition within a
rational range. Hence, we will present some feasible solutions
with real significance for solving these problems.
3. SOLID-STATE ELECTROLYTES INTERFACE
In this section, we mainly focus on the interface engineering
between the inorganic ceramic electrolyte and electrode. As we
known, there are two types of interfaces in SSMBs, including
the cathode/electrolyte interface and the anode/electrolyte
interface, and each of them has its own structural features and
shortcomings. The rigid cathode/electrolyte interface via
point-to-point contact seriously hindered the Na+ conduction
and mass transfer process.114 The unstable anode/electrolyte
interface triggered a series of irreversible side reactions and
uncontrollable dendrite growth.60,93,115,116 In addition, there is
another type of interphase, that is, the tough ISE interphase
among the ceramic particles, which greatly increases the grain-
boundary resistance. For ISEs, the Na+ conduction on the
grain boundary is the rate-limiting step, which directly
determines the total ionic conductivity of SSEs.28 In this
section, we make an overview for the two interfaces in SSMBs
to explain their critical role in boosting the electrochemical
performance and put forward our own views and opinions to
design new electrolyte interfaces at the end of this section.
3.1. Cathode/Electrolyte Interface. For an inorganic
ceramic electrolyte, although it has high ionic conductivity,
wide operating voltage, and excellent thermal stability, the rigid
cathode/electrolyte interface by point-to-point contact severely
hindered the Na+ diffusion from the cathode to ceramic
electrolyte, resulting in a large interfacial resistance, poor
interfacial compatibility and insufficient interfacial con-
tact.29,63,117 During repeated Na+ insertion and extraction,
the cathode will be pulverized and the transport paths will be
blocked entirely, leading to a restricted charge-transfer/mass-
transfer process and a severe degradation of sodium storage
performance. However, until now, the chemical compatibility
between the cathode and the SSE has not been investigated
clearly. Therefore, constructing a stable interlayer is very
necessary to optimize the cathode/electrolyte interface. At
present, the widely used strategies for promoting the interfacial
compatibility of the cathode/electrolyte interface mainly focus
on the following two aspects: (1) Fabrication of the composite
cathode material: As shown in Figure 8a, the effective contact
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area between cathode and SSE can be increased obviously after
mixing the active cathode material with ceramic particles.63,89
In comparison to the interfacial compatibility of the cathode/
SSE, the good interfacial contact should be guaranteed first,
which is the prerequisite to realize the optimized interfacial
structure. For instance, Seznec’s group developed a new
composite cathode by a facile mechanical mixing method,80
which was composed of Na3V2(PO4)3 (NVP) active material
and a NZSP ceramic electrolyte. The results elucidated that the
all-solid-state symmetric batteries of NVP−NZSP/NZSP/
NVP−NZSP presented a remarkable stability and favorable
reversibility at 200 °C. However, facile mechanical mixing is far
from enough to form the void-free composite cathode with
intimate contact, which is because both the cathode and the
ceramic electrolyte are rigid particles. (2) Introduction of an
interfacial wetting layer: A dense and stable interlayer is
formed between the cathode and the SSE by dropping the
liquid electrolyte, ionic liquid, infiltrating with polymer, or in
situ heat treatment (Figure 8b).89 In comparison to the organic
liquid electrolyte, the ionic liquid shows a higher application
value as a result of the non-volatility, non-flammability,
excellent thermal/electrochemical stability, and high ionic
conductivity. For example, a toothpaste-like composite cathode
consisting of active material Na0.66Ni0.33Mn0.67O2, Super P, and
ionic liquid PY14FSI was fabricated via a non-sintered method
by Hu’s group.118 As an outstanding wetting agent, the
functional ionic liquid can not only serve as a binder to build a
mixed conducting network to accelerate the ion/electron
transport but also change the contact mode among the rigid
particles from point contact to area contact. The composite
cathode, Na−β″-Al2O3 ceramic pellet, and sodium metal anode
were assembled into SSMBs to estimate the electrochemical
performance at 70 °C, which exhibited an ultralong cycling
stability with a capacity retention of 90% after 10 000 cycles at
6 C rate; when the current rate was back to 0.1 C, a high
capacity of 79 mAh g−1 was still kept, demonstrating excellent
reversibility.
The two strategies mentioned above have been extensively
applied to optimize the cathode/SSE interface and have
improved the interfacial compatibility to a certain extent, but
the interfacial stability between the cathode material and the
SSE should be further strengthened against the failure of
SSMBs during the electrochemical cycles. Furthermore,
researchers should pay more attention to the fundamental
research, especially in the interface engineering. By construct-
ing a new cathode/SSE interface with optimized interfacial
contact, continuous ionic and electric conducting network, and
excellent mechanical performance, the electrochemical stability
of SSMBs could be radically promoted.
3.2. Anode/Electrolyte Interface. Even if all-solid-state
batteries are safer than organic liquid batteries, the sodium
metal anode with high activity can react with most SSEs, which
can trigger a series of inevitable side reactions and produce
undesirable by-products at the anode/electrolyte inter-
face.63,93,119 Meanwhile, many studies have shown that sodium
dendrites can be observed in the SSMBs, which indicate that
the ISE could not suppress the dendrite growth to-
tally.42,120−123 Sodium dendrites can grow along the grain
boundaries, voids, and other soft places of the SSEs and
penetrate it eventually, leading to a short circuit and failure of
SSMBs.124,125 To address these tough questions, several efforts
have been dedicated to inhibit the growth of sodium
dendrites.93,126 As one of the most widely used strategy,
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 Table 1. Performance Comparison of Representative Sodium-Based SSEs
ionic voltage
conductivity activation window
type material (S cm−1)a energy (eV) (V) advantage disadvantage reference
polymer PEO12−NaFSI 3.7 × 10−6 −b − excellent flexibility, good interface contact, low ionic conductivity, limited potential window, 107
Energy & Fuels

based PTMC5−NaClO4 ∼10−6 − ∼4.2 and excellent film-forming ability and insufficient mechanical strength 128
PMA/PEG−NaClO4 + 5 wt % α-Al2O3 1.46 × 10−4 0.38 4.5 44
(70 °C)
PEO20−NaClO4−5 wt % SiO2 8.4 × 10−5 − ∼4.2 53
β/β″-Al2O3 β″-Al2O3 0.2−0.4 − − high ionic conductivity poor interface contact and inferior moisture 66
(300 °C) stability
Na−β″-Al2O3 + 0.8 wt % MgO 0.264 (400 °C) 0.21 − 67
Na−β″-Al2O3 + 0.25 wt % NiO 0.066 (350 °C) 0.166 − 73
Na−β″-Al2O3 + 1 wt % Nb2O5 0.153 (300 °C) − − 72
NASICON NZSP 5.6 × 10−4 − − high stability, wide voltage window, and high poor interface contact and expensive production 35
NZSP + 5 wt % ATO 1.43 × 10−3 − 4.6 ionic conductivity cost 129
Na3.4Sc0.4Zr1.6Si2PO12 4.0 × 10−3 0.26 ∼6 130
Na3.3Zr1.7La0.3Si2PO12 3.4 × 10−3 0.291 − 89
Na3.4Zr1.9Zn0.1Si2.2P0.8O12 5.27 × 10−3 ∼6 35
sulfide cubic Na3PS4 2 × 10−4 − − easy preparation, high conductivity, and low inferior compatibility and poor ambient stability 104
Na2.9375PS3.9375Cl0.0625 4.3 × 10−4 − − grain-boundary resistance 131
Na3SbS4 1.1 × 10−3 0.20 − 101
Na3PSe4 1.16 × 10−3 0.21 − 94

K
Na11Sn2PS12 1.4 × 10−3 0.25 − 132
CSE 63NZSP:37(PEO0.87NaI0.13) ∼10−4 − 4.64 excellent interface compatibility and good limited ionic conductivity 108
ipn-PEA + NZSP/PVDF−HFP 1.32 × 10−4 0.23 4.4 malleable property 50
pubs.acs.org/EF

(60 °C)
NZSP−PEO12−NaFSI 1.3 × 10−3 − ∼4.4 107
(80 °C)
90(PEO8−NaClO4)−10NZSP 2 × 10−4 − 4.7 26
(55 °C)
PEO−SN−NaClO4|PAN−NZSP−NaClO4 1.36 × 10−4 0.33 ∼4.8 18
a
The ionic conductivities are measured under room temperature unless stated otherwise. bThe mark “−” represents not mentioned in the reference.
Review

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Energy & Fuels
constructing a favorable interlayer between SSE and sodium
anode is an effective and practical method.119 The interlayer
can not only serve as a mechanical barrier to suppress the
dendrite growth, but also greatly promote the interfacial
contact to reduce the interfacial resistance.93,120 For example, a
molecular layer deposition alucone film was developed to
stabilize the sodium anode/SSE interface by Sun and co-
workers (Figure 8c).93 Figure 8d shows the 3D rendering
models of Na/150C alucone based on the time-of-flight
secondary ion mass spectrometry (ToF-SIMS) result, which
illustrated the uniform dispersion of the Na metal and alucone
film. After the 150 cycle alucone film (over 50 nm) was coated
on the sodium metal anode, the decomposition of the sulfide-
based electrolyte and the formation of sodium dendrites can be
significantly inhibited. Profiting from the initial activation
process, the fresh alucone film can be partly sodiated to form a
sodiation gradient along the thickness (Figure 8e), which
greatly enhanced the interfacial protection and decreased the
interfacial resistance, leading to an improved electrochemical
performance at room temperature (Figure 8f). Goodenough
and co-workers fabricated a thin interlayer formed in situ or
introduced a dry polymer film between the Na anode and the
NASICON electrolyte.127 After introduction of the polymer
interlayer, the ability of prohibiting the sodium dendrites
increased remarkably (panels g and h of Figure 8). The good
wettability of Na metal on the NASICON pellet endowed a
uniform Na+ flux across the polymer interlayer. As a result, the
SSMBs displayed superior cycling performance and high
coulombic efficiency. In addition, Li and co-workers reported
the direct growth of the graphene-like interlayer on the
NASICON electrolyte (G−NASICON) via a chemical vapor
deposition method.126 As shown in panels i and j of Figure 8,
the thickness of the graphene-like interlayer can be tailored by
adjusting the preparation parameters. Owing to the abundant
defects in the graphene-like interlayer, the Na+ flux distribution
can be homogeneously regulated during the repeated Na
plating/stripping process, resulting in a dendrite-free sodium
anode. Meanwhile, the graphene-like coating can greatly
decrease the NASICON/Na interfacial resistance by 10
times. Thus, the Na/G−NASICON/Na symmetric cells
displayed excellent plating/stripping performance for 1000 h
at 1 mA cm−2 with a capacity of 1 mAh cm−2 (Figure 8k).
In short, the growth of sodium dendrites always restricts the
development and application of SSMBs. It is essential to
develop new strategies that can not only reduce the interface
resistance by increasing the effective contact area between SSE
and sodium metal anode but also regulate the deposition
behavior of Na+ on the sodium anode to constrain the growth
of sodium dendrites. Furthermore, the novel interlayer should
also have comprehensive properties, including excellent
chemical stability, good wettability with sodium metal anode,
high flexibility and appropriate strength. By designing high-
performance interlayer between SSE and sodium anode, the
electrochemical stability of SSMBs will be promoted
significantly.
In the above sections, a comprehensive review about
sodium-based SSEs has been summarized in detail and
provided the specific improvement measures pertinently. In
addition, to deeply understand the advantage/disadvantage of
different types of SSEs, a detailed performance comparison of
representative sodium-based SSEs has been summarized in
Table 1, including Na+ conductivity, activation energy, voltage
window, chemical/electrochemical stability, and interface
pubs.acs.org/EF Review
compatibility. We believe that this review can give a valuable
reference for developing advanced SSMBs.
4. CONCLUSION AND PERSPECTIVES
In this review, we outline the recent progress of the sodium-
based SSEs, elaborate the potential Na+ transport mechanisms,
point out the individual challenges, and put forward the
relevant improvement strategies for promoting the interfacial
compatibility and enhancing the ionic conductivity purposely.
In addition, we critically evaluate the recent works on
preparing technology, structural advantages, and performance
parameters for sodium-based SSEs. Finally, some new
perspectives for developing next-generation advanced SSEs
toward safe and high-performance SSMBs are provided as
follows: (1) Constructing novel CSEs with continuous 3D Na+
conduction framework: To improve the interfacial compati-
bility between the ISE and the electrode and elevate the room-
temperature ionic conductivity of the SPE, the “polymer-in-
ceramic” strategy should be applied to deal with these thorny
problems by integrating the ISE with high ionic conductivity
and SPE with excellent flexibility into a composite SSE.
Furthermore, it is essential to construct a 3D interconnected
ceramic framework with unique micro/nanostructure, which
can not only offer continuous and fast Na+ transport pathways
to promote the Na+ diffusion kinetics but also enhance the
thermal/electrochemical stability of the CSE. After infusion of
the polymer/sodium salt slurry into the voids of the 3D
ceramic framework, the interfacial compatibility between CSE
and electrode can be significantly promoted from rigid contact
(point-to-point) to interfacial contact. Therefore, the syner-
gistic effect of CSE can be fully exerted via constructing a novel
CSE with a continuous 3D Na+ conduction framework. (2)
Revealing the potential Na+ transport mechanisms: By far, the
potential Na+ transport mechanisms of SSEs have not been
fully elucidated, including conduction behavior, transfer paths,
internal interaction, and parameter manipulation. Under-
standing the Na+ conduction behavior and transfer paths in
SSEs are crucial to excavate the intrinsic relation between the
phase structure of SSEs and the Na+ conduction, which is
favorable to design new types of SSEs with high ionic
conductivity. In addition, revealing the internal interaction
between Na+ and SSE matrix is another essential factor to
optimize the configuration and composition of the SSEs. (3)
Exploring the new types of SSE systems: Although many kinds
of SSE materials were successively reported in recent decades,
the interfacial compatibility issues have not been resolved
effectivity and the sodium dendrites have not been completely
suppressed. Thus far, the facile aliovalent substitution strategy
has been unable to cope with these challenges above. As a
result, great efforts should be made to explore the new SSE
systems, such as novel CSE with continuous 3D Na+
conduction framework, electrolyte/electrode integral construc-
tion, functional gradient materials, multilayer ceramic electro-
lyte, and artificial SEI layer, etc. By designing novel SSEs with
excellent comprehensive performance, the electrochemical
stability of SSEs will be significantly improved. (4) Developing
advanced in situ characterization techniques with high space
and time resolution: At present, the development of SSEs is
still in the initial stage, and many issues have not been resolved.
As we know, the Na+ conduction in SSEs is a dynamic process
with time-resolved behavior, as a result, the intermediate states
are too quick to be captured by the traditional characterization
techniques, leading to the loss of some critical instantaneous
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Energy & Fuels
information. More importantly, the Na+ transport mechanism
is strongly dependent upon these complex kinetic processes of
the intermediate states. Therefore, it is urgent to develop
advanced in situ characterization techniques to realize the real-
time monitoring and dynamic tracking for Na+ in SSEs. By
coupling the in situ morphology observation and phase
analysis, the underlying relationship between structural
evolution and phase composition may be excavated deeply in
the process of electrochemical reaction. (5) Combining
theoretical calculations with numerical simulation: Because
the crystal structures of inorganic ceramic electrolytes with
high ionic conductivity possess long-range periodicity and
symmetry, their structural and performance characteristics are
easier to calculate than the polymer electrolyte. Thus, most of
the current theoretical computation and numerical simulation
are based on the ISEs. To realize accurate prediction of ionic
conductivity, some essential parameters should be evaluated by
theoretical calculations, including internal transport barrier,
carrier concentration, defect concentration, diffusion coef-
ficient and mobility of Na+; all of these factors are certainly
important for estimating the ionic conductivity, which can
fundamentally uncover the essence of the regulating effect for
enhancing the ionic conductivity. In comparison to the
conventional preparation methods, the computational simu-
lation greatly shortens the preparation time and reduces the
production cost of the SSEs. Furthermore, high-throughput
screening technology should also be conducted to optimize the
composition and ratio of SSEs toward optimum performance.
Under the guidance of the first-principle calculation, the
chemical kinetic principle and internal diffusion theory of Na+
in SSEs are expected to be further elaborated and perfected in
the future.
■
AUTHOR INFORMATION
Corresponding Authors
Yuchang Si − Logistics University of People’s Armed Police
Force, Tianjin 300309, People’s Republic of China;
Email: siyuch@163.com
Lifang Jiao − Key Laboratory of Advanced Energy Materials
Chemistry (Ministry of Education), College of Chemistry,
Nankai University, Tianjin 300071, People’s Republic of
China; orcid.org/0000-0002-4676-997X; Email: jiaolf@
nankai.edu.cn
Authors
Zhaopeng Li − Key Laboratory of Advanced Energy Materials
Chemistry (Ministry of Education), College of Chemistry,
Nankai University, Tianjin 300071, People’s Republic of
China
Pei Liu − Key Laboratory of Advanced Energy Materials
Chemistry (Ministry of Education), College of Chemistry,
Nankai University, Tianjin 300071, People’s Republic of
China
Kunjie Zhu − Key Laboratory of Advanced Energy Materials
Chemistry (Ministry of Education), College of Chemistry,
Nankai University, Tianjin 300071, People’s Republic of
China
Zhaoyuan Zhang − Key Laboratory of Advanced Energy
Materials Chemistry (Ministry of Education), College of
Chemistry, Nankai University, Tianjin 300071, People’s
Republic of China
Yijing Wang − Key Laboratory of Advanced Energy Materials
Chemistry (Ministry of Education), College of Chemistry,
pubs.acs.org/EF Review
Nankai University, Tianjin 300071, People’s Republic of
China; orcid.org/0000-0002-9584-5406
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.energyfuels.1c00347
Notes
The authors declare no competing financial interest.
Biographies
Zhaopeng Li received his master’s degree in the School of Materials
and Energy from Guangdong University of Technology (China) in
2019. At present, he is a Ph.D. student in the group of Prof. Lifang
Jiao at Nankai University. His research interests mainly focus on the
design and fabrication of high-performance electrode material and
solid-state electrolyte for rechargeable lithium/sodium-ion batteries.
Pei Liu received her B.S. degree in chemistry from Nankai University
(China) in 2018. At present, she is a Ph.D. student under the
supervision of Prof. Lifang Jiao at Nankai University (China). Her
research currently focuses on the design and preparation of advanced
metal anode protection for rechargeable sodium batteries.
Kunjie Zhu received his B.S. (2015) and M.S. (2018) degrees in the
School of Material Science and Engineering from Central South
University in China. Currently, he is a Ph.D. student in the group of
Prof. Lifang Jiao at Nankai University. His research interest mainly
focuses on the design of novel nanomaterials and their applications for
energy storage and conversion.
Zhaoyuan Zhang is currently an undergraduate student at Nankai
University. He is a trainee in Lifang Jiao’s group, assisting the graduate
students to do related experiments.
Yuchang Si is currently a professor at Logistics University of People’s
Armed Police Force, China. He received his Ph.D. degree under the
supervision of academician Yusheng Yang from the Research Institute
of Chemical Defense (China) in 2013. His current research interests
are in the design and synthesis of advanced materials for energy
conversion and storage applications.
Yijing Wang obtained her B.Sc. (1989) and Ph.D. (2000) degrees
from Nankai University and worked as a postdoctoral fellow at Tokyo
University, Japan, during 2000−2004. Since 2008, she has been a
professor in the College of Chemistry, Nankai University. Her
research interests include hydrogen storage and high-performance
electrode materials.
Lifang Jiao is a professor at Nankai University, China. She received
her Ph.D. degree from Nankai University (China) in 2005. She has
co-authored over 200 relevant peer-reviewed publications with a h-
index of 58. Her current research is focused on energy conversion and
storage (including lithium, sodium, and potassium secondary
batteries) and electrocatalytic hydrogen evolution.
■
ACKNOWLEDGMENTS
This work was financially supported by the National Natural
Science Foundation of China (52025013, 52071184, and
21835004), the Ministry of Science and Technology of China
(2017YFA0206702 and 2016YFB0901502), the 111 Project
(B12015), the Natural Science Foundation of Tianjin
(18ZXJMTG00040 and 19JCZDJC31800), and the Funda-
mental Research Funds for the Central Universities.
■
DEDICATION
This work is dedicated to the 100th anniversary of chemistry at
Nankai University.
M https://doi.org/10.1021/acs.energyfuels.1c00347
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Energy & Fuels
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pubs.acs.org/EF
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